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WO2018165583A1 - Matériau optique non linéaire - Google Patents

Matériau optique non linéaire Download PDF

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Publication number
WO2018165583A1
WO2018165583A1 PCT/US2018/021802 US2018021802W WO2018165583A1 WO 2018165583 A1 WO2018165583 A1 WO 2018165583A1 US 2018021802 W US2018021802 W US 2018021802W WO 2018165583 A1 WO2018165583 A1 WO 2018165583A1
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nlo
crystal
exhibits
nonlinear optical
aspects
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PCT/US2018/021802
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English (en)
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P. Shiv Halasyamani
Hongwei Yu
Hongping Wu
Weiguo Zhang
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University Of Houston System
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Priority to US16/492,261 priority Critical patent/US11262640B2/en
Publication of WO2018165583A1 publication Critical patent/WO2018165583A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/3551—Crystals
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/48—Halides, with or without other cations besides aluminium
    • C01F7/50—Fluorides
    • C01F7/54—Double compounds containing both aluminium and alkali metals or alkaline-earth metals
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B17/00—Single-crystal growth onto a seed which remains in the melt during growth, e.g. Nacken-Kyropoulos method
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/12—Halides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/60—Compounds characterised by their crystallite size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

Definitions

  • Nonlinear optical (NLO) materials may be employed for applications including optical switching and power limitation as well as image processing and manipulation.
  • NLO behavior is the behavior of light in nonlinear materials where the dielectric polarization has a nonlinear response to the electric field of light applied, for example, when the electric field may be of an interatomic strength.
  • a solid-state laser of a specific wavelength may be about 1064 nm (infrared), as compared to visible light which is from roughly 400 nm (blue) to 700 nm (red).
  • SHG second-harmonic generation
  • KBBF has both manufacturing and application challenges issues. For example, (1) To synthesize KBBF, BeO must be employed, and BeO is highly toxic and may have restrictions on experimentation and use; (2) Even though KBBF was discovered in the late 1990's, the largest crystal grown to date is 4mm due to the layered structure of the material; and (3) KBBF was discovered overseas and exports of the material have been constrained or halted because of its technological applications.
  • NLO nonlinear optical
  • NLO nonlinear optical material
  • nonlinear optical material selected from the group consisting of KSrC0 3 F Rb 3 Ba 3 Li 2 Al4B 6 02oF and KsSrsLijA B ⁇ oF.
  • FIG. 1 is a powder x-ray diffraction (PXRD) graph of poly crystalline K 3 Sr 3 Li 2 Al 4 B 6 0 2 oF fabricated according to certain aspects of the present disclosure.
  • PXRD powder x-ray diffraction
  • FIG. 2 is a schematic illustration of how the the AIO4 and Li0 3 F tetrahedra connect with isolated BO 3 triangles to create [Li 2 Al 4 B 6 0 2 oF]oo double-layers according to certain aspects of the present disclosure.
  • FIG. 3 is as schematic illustration of the ab-plane of an NLO material fabricated according to certain aspects of the present disclosure.
  • FIGS. 4A and 4B are graphs of the powder SHG results for K 3 Sr 3 Li 2 Al 4 B 6 0 2 oF fabricated according to aspects of the present disclosure.
  • FIG. 5 is an indexed single crystal of K 3 Sr 3 Li 2 Ai 4 B 6 0 2 oF fabricated according to aspects of the present disclosure.
  • FIG. 6 is a graph of the refractive-index for a wafer of K 3 Sr 3 Li 2 Al 4 B 6 0 2 oF that was manufactured according to certain aspects of the present disclosure.
  • FIG. 7 is a graph of the calculated refractive index dispersion curves, based on the Sellmeier equations, for the samples of K 3 Sr 3 Li 2 Al 4 B 6 0 2 oF manufactured according to certain aspects of the present disclosure.
  • FIG. 8 is a schematic illustration of the structural evolution from KBBF to Rb 3 Ba 3 Li 2 Al 4 B 6 0 2 oF.
  • FIGS. 9A-9C illustrate a thermogravimetric/differential thermal analysis (TG/DTA) curve, a recrystallization curve, and a photo of a crystal of Rb 3 Ba 3 Li2Al4B602oF fabricated according to aspects of the present disclosure.
  • TG/DTA thermogravimetric/differential thermal analysis
  • FIGS. 10A-10D are schematics of the building blocks and as-fabricated structure of
  • FIGS. 11A-11D illustrate linear and non-linear optical properties of
  • FIG. 12 illustrates a graph of the IR spectrum of Rb 3 Ba 3 Li 2 Al 4 B 6 0 2 oF fabricated according to certain aspects of the present disclosure.
  • FIG. 13 is a graph of the IR Spectrum of Li 2 K 3 Sr 3 Al 4 B 6 0 2 oF fabricated according to certain aspects of the present disclosure.
  • FIG. 14 is a graph of the TG/DTA data for Li 2 K 3 Sr 3 Al 4 B 6 0 2 oF fabricated according to certain aspects of the present disclosure.
  • FIGS. 15A and 15B are before (15 A) and after (15B) images of a high quality Rb 3 Ba 3 Li 2 Al 4 B 6 02oF crystal fabricated according to certain aspects of the present disclosure that was placed in water for a week with no decomposition or degradation observed.
  • FIG. 16 is a graph of transmission and wavelength for K 3 Sr 3 Li 2 Al4B 6 02oF fabricated according to certain aspects of the present disclosure.
  • a "laser damage threshold” is a term used herein to define a peak fluency of laser irradiation at which irreversible changes in a material's structure may occur.
  • This laser damage threshold may be defined as the highest quantity of laser radiation that a material may absorb before there are changes to the material's optical properties. This may also be defined by the ISO standards 21254-1, 2, 3, and 4 definitions as the highest quantity of laser radiation incident upon the optical component for which the extrapolated probability of damage is zero where the quantity of laser radiation may be expressed as power density, linear power density or energy density.
  • Anisotropy is the term used to define properties/characteristics of material that may vary depending upon the direction in which the properties/characteristics are observed/measured.
  • Non-centrosymmetric is a term used to describe the symmetry (or lack thereof) of certain crystal structures. Non-centrosymmetric materials are materials where point groups lack an inversion center, in contrast to centrosymmetric structures and materials which comprise a unit cell (e.g., face-centered-cubic, "fee") that has a center of symmetry at, for example, (0,0,0).
  • the inversion centers may be observed at atom sites such as the atom at (0, 0, 1 ⁇ 2), which would invert to the atom at (0, 0, -1 ⁇ 2), and the atom at (1 ⁇ 2,1 ⁇ 2, 0) inverts to (-1 ⁇ 2, -1 ⁇ 2, 0). While an fee structure comprises an inversion center at every atom, a structure may be characterized as centrosymmetric if it comprises at least one inversion center and may be characterized as non-centrosymmetric if it does not comprise any inversion centers.
  • Bin gap is the characteristic of a material, such as an optical material, that is associated with the minimum energy needed to move an electron from a bound state (valence band) into a free state (conduction band). Varying energy band structures in semiconductors are associated with the electrical (including thermoelectric) properties exhibited by these semiconductors.
  • NLO materials are of intense interest owing to their ability to control and manipulate light for the generation of coherent radiation at a variety of difficult to access wavelengths. They have efficiently expanded the spectral ranges of solid state lasers from ultraviolet (UV) to infrared (IR). Accessing directly the deep-ultraviolet (DUV) region (150 nm - 400 nm), however, is especially challenging, yet desirable for a number of advanced optical technologies, including photolithography for microelectronics and attosecond pulse generation for electron dynamic studies in matter.
  • UV ultraviolet
  • IR infrared
  • the NLOs of the present disclosure exhibit at least one of the following desirable characteristics: i) a noncentrosymmetric (NCS) crystal structure; ii) large SHG coefficient (dy > 0.39 pm/V); iii) wide band gap (E g > 6.2 eV), i.e. an absorption edge ⁇ 200 nm; iv) moderate birefringence at 1064nm (d n - 0.05 - 0.09); v) chemical stability with a large laser damage threshold (LDT > 5.0 gigawatts per cm 2 or GW/ cm 2 ), and vi) easy growth of large - centimeter size - high quality single crystals.
  • NCS noncentrosymmetric
  • NLOs of the present disclosure exhibit at least two, alternatively at least three or alternatively at least four of the following desirable characteristics: i) a noncentrosymmetric (NCS) crystal structure; ii) large SHG coefficient (dy > 0.39 pm/V); iii) wide band gap (E g > 6.2 eV), i.e. an absorption edge ⁇ 200 nm; iv) moderate birefringence at 1064nm (d n ⁇ 0.05 - 0.09); v) chemical stability with a large laser damage threshold (LDT > 5.0 GW/cm 2 ), and vi) easy growth of large - centimeter size - high quality single crystals.
  • NCS noncentrosymmetric
  • the NLO materials of the present disclosure are used in UV and/or DUV applications and exhibit the following characteristics : i) a noncentrosymmetric (NCS) crystal structure; ii) large SHG coefficient (dy > 0.39 pm/V); iii) wide band gap (E g > 6.2 V), i.e. an absorption edge ⁇ 200 nm; iv) moderate birefringence at 1064 nm (d n ⁇ 0.05 - 0.09); v) chemical stability with a large laser damage threshold (LDT > 5.0 GW/cm 2 ), and vi) easy growth of large - centimeter size - high quality single crystals.
  • NCS noncentrosymmetric
  • the systems and methods disclosed herein produce NLO materials that have a small walk-off effect and are not hygroscopic.
  • walk-off effect refers to a material having too large a birefringence ( ⁇ > 0.11) resulting in a reduction in the intensity of the second-harmonic beam and the birefringence may be determined through refractive index measurements.
  • An NLO material of the type disclosed herein may be characterized by a walk-off of from about 1 mrad to about 200 mrad, alternatively from about 10 mrad to about 65 mrad or alternatively from about 15 mrad to about 32 mrad.
  • the NLO materials of the present disclosure comprise KSrCOsF, K 3 Sr 3 Li 2 Al4B 6 02oF or Rb 3 Ba 3 Li 2 Al 4 B 6 02oF, each of which are characterized by the presence of usable band gaps and birefringence.
  • the NLO materials of the present disclosure comprise KSrCOsF, K 3 Sr 3 Li 2 Al4B 6 02oF or Rb 3 Ba 3 Li 2 Al 4 B 6 02oF which display (i) moderate birefringence (i.e. ⁇ 0.06 ) (ii) no walk-off issues (iii) are non-hygroscopic and (iv) form large, high quality single crystals.
  • a crystal suitable for use in the present disclosure has a minimum diameter of about 2 mm in at least two directions (e.g., the smallest dimension that is not a thickness is greater than 2mm), alternative from about 2 mm to about 20 mm alternatively from about 3 mm to about 15 mm or alternatively from about 5 mm to about 10 mm.
  • the NLO materials of the present disclosure may form high quality crystals wherein the term "high quality” as used herein refers to a crystal that is optically clear and exhibits a full-width half-maximum (FWHM) of a Bragg reflection of ⁇ 100" (arc seconds).
  • the NLO materials of the present disclosure form high quality single crystals with minimum diameters in the ranges disclosed herein.
  • a NLO of the present disclosure has the general formula XLi 2 Al 4 B 6 02oF wherein X comprises potassium (K) and strontium (Sr), alternatively X comprises K 3 Sr 3 In an aspect, X comprises rubidium (Rb) and barium (Ba), alternatively, X comprises Rb 3 Ba 3 .
  • KSrCC ⁇ F a nonlinear optical material that can generate 266 nm radiation.
  • crystals of KSrCC ⁇ F do not suffer from walk-off issues and are not hygroscopic. It is to be appreciated that as the generation of 266 nm radiation through second-harmonic generation occurs by using large single crystals, powders would not be desirable for this purpose.
  • an NLO of the present disclosure comprises a crystal of KSrCOsF.
  • a crystal of KSrCOsF may be grown using any suitable methodology (e.g., top-seeded solution growth method) using KF-L12CO 3 as a flux with SrC0 3
  • the components used to prepare the NLO were used in amounts that provided a ratio of 7: 10:3 - SrC03:KF:Li2C03 in the reaction mixture which was then heated to a temperature in the range of from about 600 °C to about 700 °C alternatively from about 615 °C to about 675 °C or alternatively from about 625 °C to about 650 °C at a heating rate of from about 25 °C /hour to about 100 °C /hour for a time period of from about 12 hours to about 48 hours or alternatively from about 18 hours to about 36 hours.
  • NLO materials of the present disclosure may be present in amounts to provide ratios of SrC0 3 :KF
  • the NLO materials disclosed herein may be used as a material for converting the wavelength of laser light.
  • the NLO materials disclosed herein may be components of a device such as a laser. It should, however, be noted that the use of the NLO materials of the present disclosure is by no means limited to wavelength converting devices and it can be applied to any devices that utilize the nonlinear optical effect.
  • Other devices than wavelength converters with which the nonlinear optical material of the present invention can be used include optical bistable devices (e.g. optical memory devices, light pulse waveform control devices, photolimiters, differential amplifiers, phototransistors, A/D converters, optical logic devices, photomultivibrators and optical flip-flop circuits), optical modulators and phase conjugated optical devices.
  • FIG. 1 is a powder x-ray diffraction (PXRD) Polycrystalline K 3 Sr 3 Li 2 Al 4 B 6 0 2 oF was synthesized through solid-state methods using stoichiometric amounts of the reagents. The phase purity was confirmed by powder X-ray diffraction, the results of which are shown in FIG. 1. A single crystal of K 3 Sr 3 Li 2 Ai 4 B 6 0 2 oF was obtained through a Li 2 0-SrF 2 -B 2 03 flux, and its crystal structure was determined by single crystal X-ray diffraction (Table 1).
  • PXRD powder x-ray diffraction
  • the B + cations are coordinated to three oxygen atoms to form the B0 3 triangles.
  • the Al + and Li + atoms are bonded with four anions - four oxygen atoms for Al + and three oxygen atoms and one fluoride for Li + to form the AIO4 and Li0 3 F tetrahedra, respectively.
  • a plurality of single crystals of K 3 Sr 3 Li 2 Al 4 B 6 0 2 oF was grown from a high temperature solution using the flux.
  • the K 3 Sr 3 Li 2 Al 4 B 6 0 2 oF crystal was grown by combining a mixture of SrC0 3 (0.03 mol, 4.420 g), K 2 C0 3 (0.01-0.03 mol, 1.38-4.1463 g), Li 2 C0 3 (0.01-0.05 mol, 0.0738-3.69 g), LiF (0.01-0.05 mol, 0.259-1.295 g), H 3 B0 3 (0.1-0.3 mol, 6.183-18.549 g) and A1 2 0 3 (0.04 mol, 4.078 g).
  • the mixture was melt at 850 °C and held at this temperature for 20 h to form a homogeneous melt.
  • the melt quickly cooled down to 750-700 °C, a platinum wire was promptly dipped into melt.
  • the temperature was further decreased to 700-650 °C at a rate of 5 °C/d, then the platinum wire was pulled out of the melt and allowed to cool to room temperature at a rate of 20 °C/h. Colorless, transparent crystals were grow in in this manner.
  • a Be-free deep-ultraviolet nonlinear optical material K 3 Sr 3 Li 2 Al 4 B 6 0 2 oF has been successfully synthesized herein.
  • K 3 Sr 3 Li 2 Al 4 B 6 0 2 oF possess a short cut-off edge, - 190 nm, and the SHG responses are 1.7xKH 2 P0 4 and 0.3x ?-BaB 2 O4 at 1064 and 532 nm incident radiation, respectively.
  • the refractive indices measurement reveals a suitable birefringence of 0.0616 at 532 nm.
  • FIG. 1 is a powder x-ray diffraction graph of the actual, experimental, and calculated PXRD patterns, which are in good agreement.
  • the crystals of K 3 Sr 3 Li 2 Al 4 B 6 0 2 oF were grown from a high temperature solution using the flux.
  • the K 3 Sr 3 Li 2 Ai 4 B 6 0 2 oF crystal was grown by combining a mixture of SrC0 3 (0.03 mol, 4.420 g), K 2 C0 3 (0.015 mol, 2.073 g), Li 2 C0 3 (0.025 mol, 1.845 g), LiF (0.02 mol, 0.518 g), H 3 B0 3 (0.1 mol, 6.183 g) and A1 2 0 3 (0.01 mol, 1.01 g).
  • the mixture was melt at 850 °C and held at this temperature for 20 h to form a homogeneous solution.
  • the solution quickly cooled down to 750 °C, a platinum wire was promptly dipped into solution.
  • the temperature was further decreased to 700 °C at a rate of 5 °C/d, then the platinum wire was pulled out of the solution and allowed to cool to room temperature at a rate of 20 °C/h.
  • Colorless, transparent crystals that used for the seed crystal had crystallized on the platinum wire.
  • a plurality of large single crystals were grown by TSSG method by the Li 2 0-SrF 2 -B 2 0 3 flux.
  • the K 3 Sr 3 Li 2 Al 4 B 6 0 2 oF crystal was grown by combining a mixture of SrC0 3 (0.2 mol, 29.46 g), K 2 C0 3 (0.075 mol, 10.37 g), Li 2 C0 3 (0.125 mol, 9.24 g), LiF (0.1 mol, 2.59 g), H 3 B0 3 (0.35 mol, 21.64 g) and A1 2 0 3 (0.05 mol, 5.05 g).
  • the mixture was melted at 850 °C and held at this temperature for 24 h to form a homogeneous solution.
  • the solution was cooled down to 750 °C at a rate of 20 °C/h.
  • the Pt wire was dipped into the solution for 30 minutes to determine the saturation temperature.
  • a saturation temperature of 720 °C was determined by introducing a K 3 Sr 3 Li 2 Al 4 B 6 0 2 oF seed crystal to the solution and holding it for 48h. During this time the seed crystal did not grow or dissolve, and no additional crystals were formed.
  • a K 3 Sr 3 Li 2 Al4Be0 2 oF seed crystal was introduced into the solution at 725 °C and held for 2h that allowed the seed crystal surface to solution.
  • the solution was cooled to the saturation temperature, 720 °C, over lh.
  • a large K 3 Sr 3 Li 2 Al 4 B 6 0 2 oF crystal was gown by cooling the solution at a rate of 0.2 °C/d to 716 °C and the seed crystal rotates at 10 rpm that controls by a Crystal growth Furnace Lifting Structure.
  • the crystal was pulled out of solution and cooled at a rate of 10 °C/h to room temperature. The total time for crystal growth was 27 d.
  • Powder SHG Measurement Powder SHG measurements were performed on a modified Kurtz-NLO system using a pulsed Nd:YAG laser (Quantel Laser, Ultra 50) with a wavelength of 1064 and 532 nm. As the powder SHG response has been shown to strongly depend on particle size, the K 3 Sr 3 Li 2 Al 4 B60 2 oF sample was ground and sieved into distinct particle size ranges ( ⁇ 20, 20-45, 45-63, 63-75, 75-90, 90-125, 125-150 ⁇ ) to investigate its phase-matching behavior. Polycrystalline KH 2 PO 4 (KDP) and ?-BaB 2 0 4 ( -BBO) were also sieved into similar particle sizes for SHG response comparison.
  • KDP Polycrystalline KH 2 PO 4
  • ?-BaB 2 0 4 -BBO
  • FIG. 12 is a graph of the transmission spectrum of K 3 Sr 3 Li 2 Al 4 B60 2 oF crystal was measured using a Shimadzu SolidSpec-3700DUV spectrophotometer from 190 to 2600 nm. A piece of (001) crystal wafer with a thickness of 1 mm was used to perform the measurement.
  • FIG. 13 is a graph of the IR Spectrum of Li 2 K 3 Sr 3 Al 4 B 6 0 2 oF. The infrared (IR) spectrum data of FIG. 13 was collected on a Thermo Nicolet Nexus 470 FTIR spectrometer from 400 to 4000 cm -1 . Table 6 illustrates the data associated with FIG. 13.
  • FIG. 2 is a schematic illustration of how the AIO4 and L1O 3 F tetrahedra connect with isolated BO 3 triangles to create [Li 2 Al 4 B 6 0 2 oF]oo double-layers that contain nine coordinated K + cations within the layer, and eight coordinated Sr 2+ cations between the layers.
  • the structure may be written as [4(A10 4/2 ) " 6(B0 3 /2)° 2(Li0 3/2 Fi /2 ) 2 5" ] 9" with charge balance retained by three K + and three Sr 2+ cations.
  • the double-layers consist of two [LiAl 2 B 3 0 6 ]oo single layers that are linked by oxygen and fluoride atoms.
  • FIG. 3 is as schematic illustration of the ab-plane of an NLO material fabricated according to certain aspects of the present disclosure.
  • the AIO4 and the L1O 3 F tetrahedra are linked to the BO 3 groups through oxygen forming rings wherein the K + cations reside.
  • the reported bond lengths are consistent with those of previously reported compounds. Bond valence calculations are consistent with the reported oxidation states (see Tables 2 and 3).
  • the IR spectrum also confirms the extence of the BO 3 and AIO4 groups (see FIG. 12).
  • Table 3 shows the bond lengths [A] and angles [deg] for Li 2 K3Sr3A B60 2 oF. Table 3:
  • FIGS. 4A and 4B are graphs of the powder SHG results for K 3 Sr 3 Li 2 Al 4 B 6 0 2 oF fabricated according to aspects of the present disclosure.
  • FIG. 14 is a graph of the TG/DTA data for Li 2 K 3 Sr 3 Al 4 B 6 0 2 oF.
  • FIG. 14 indicates an endothermic peak around 812 °C. Above 812 °C, K 3 Sr 3 Li 2 Al 4 B 6 0 2 oF decomposes to K 2 A1 2 B 2 0 7 and other unknown phases.
  • moisture stability a 0.1930 g crystal of K 3 Sr 3 Li 2 Al B6() 2 oF was submerged in water for one week. After one week the crystal was removed from the water and reweighed.
  • FIG. 5 is a photograph of an indexed single crystal of K 3 Sr 3 Li 2 Al B6() 2 oF.
  • Large single crystals of K 3 Sr 3 Li 2 Al 4 B 6 0 2 oF were grown by the top seeded-solution growth (TSSG) technique discussed herein.
  • TSSG top seeded-solution growth
  • BFDH Bravais-Friedel-Donnay-Harker
  • the calculated morphology of FIG. 5 is consistent with that of the grown crystal.
  • KBBF and SBBO is the tendency to layer along the optic axis, i.e. the oaxis, that hinders large crystal growth.
  • the crystal dimension along the oaxis is 5 mm that suggests the short double-layer distance in K 3 Sr 3 Li 2 Al 4 B 6 0 2 oF favors large crystal growth.
  • FIG. 6 is a graph of the refractive-index for a wafer of K 3 Sr 3 Li 2 Al 4 B 6 0 2 oF that was manufactured according to certain aspects of the present disclosure.
  • the sample shown in the inset in FIG. 6, was cut and polished to obtain the optical measurements in FIG. 6.
  • the transmission spectrum of K 3 Sr 3 Li 2 Al 4 B 6 0 2 oF was collected on a 1 mm thick crystal at room temperature (see experimental section).
  • FIG. 16 is a graph of transmission and wavelength for K 3 Sr 3 Li 2 Al B 6 0 2 oF fabricated according to certain aspects of the present disclosure.
  • An absorption edge of 190 nm was determined, as is shown in FIG. 16.
  • the refractive index was measured at at five wavelengths - 450.2, 532, 636.5, 829.3, and 1062.2 nm, using the prism coupling technique, in order to determine the birefringence.
  • a (001) crystal wafer was polished for the measurements, as shown in the inset in FIG. 6.
  • the calculated and experimental refractive indices and Sellmeier coefficients are given (Tables 4 and 5). The data in Tables 4 and 5 enables the determination of the birefreingence. This data is fitted using the Sellmeier quations, which are the curves in FIG. 6, and is used to determine the phase-matching wavelength range in FIG. 7.
  • FIG. 7 is a graph of the calculated refractive index dispersion curves, based on the Sellmeier equations, for the samples of K 3 Sr 3 Li 2 Ai 4 B 6 02oF manufactured according to certain aspects of the present disclosure.
  • the red solid and green dashed lines represent the calculated refractive indices for the fundamental and second harmonic wavelengths, i.e. n(co) and n(2co), whereas the blue dashed line represents (n 0 (co) + n e (co))/2.
  • K 3 Sr 3 Li 2 Al 4 B 6 02oF is type I phase-matchable for fundamental (second-harmonic) radiation from 448 - 4970 nm (224 - 2485 nm).
  • K 3 Sr 3 Li2Al4B602oF The type II phase-matching wavelength range for fundamental (second- harmonic) radiation is 670 - 3904 nm (335 - 1952 nm).
  • the SHG limit for K 3 Sr 3 Li2Al4B602oF is 224 nm, indicating that the material can achieve FHG and produce 266 nm light from 1064 nm laser.
  • K 3 Sr 3 Li 2 Al 4 B 6 02oF may be a viable replacement for ⁇ - BaB 2 04 and CsLiB 6 Oio
  • NLO KBe 2 B0 3 F 2 (KBBF) and Sr 2 Be2B 2 0 7 (SBBO)
  • K 3 Sr 3 Li 2 Al 4 B 6 02oF were fabricated.
  • the NLO active material exhibits an absorption edge of 190 nm, and is SHG active at 1064 nm and 532 nm. Large single crystals were grown using the top-seeded solution growth method. Optical measurements on these crystals revealed a moderate birefringence of 0.0574 at 1064 nm.
  • a relatively large seed was attached to the platinum rod and was soaked in the solution. By observing the growth or dissolution of the seed, a saturation temperature of 712 °C was determined. Then a high quality Rb 3 Ba 3 Li 2 Al 4 B 6 0 2 oF seed was dipped into the surface of the solution at 10 °C higher than the saturation temperature. This was followed by decreasing the temperature to the saturation point over 40 min. From this temperature, the solution was cooled at a rate of 0.25 °C per day. After the desired crystal size was obtained, the Rb 3 Ba 3 Li 2 Al 4 B 6 0 2 oF crystal was pulled out of the solution and cooled to room temperature at a rate of 10 °C/h.
  • a crystal of KSrCC ⁇ F was grown by the top-seeded solution growth method using KF- L12CO 3 as a flux.
  • KF, SrCC>3, and L12CO 3 with a molar ratio 10:7:3 were placed in an alumina crucible, heated to 630 °C at a heating rate of 100 °C/h and held for 50 h in order to form a homogenous melt.
  • Crystals of KSrCC ⁇ F were first grown by spontaneous crystallization, i.e. crystals formed on an alumina rod dipped into the melt. Seed crystals were selected from these spontaneously grown crystals.
  • a crystallization temperature of 611°C was determined by observing the growth or dissolution of the seed crystals when dipped into the melt.
  • An oriented seed crystal was introduced into the melt at a rotation rate of 5 rpm at 2 °C higher than the crystallization temperature of 611°C in order to reduce surface defects of the seed.
  • the temperature was decreased to the crystallization temperature at a cooling rate of 0.5 0 C/min. From the crystallization temperature, the melt was cooled at a rate of 0.5 °C per day to 590 °C.
  • FIG. 12 illustrates a graph of the IR spectrum of Rb 3 Ba 3 Li 2 Al 4 B 6 0 2 oF fabricated according to certain aspects of the present disclosure.
  • a relatively large seed was attached to the platinum rod and was soaked in the solution. By observing the growth or dissolution of the seed, a saturation temperature of 712 °C was determined. Then a high quality Rb 3 Ba 3 Li 2 Al 4 Be0 2 oF seed was dipped into the surface of the solution at 10 °C higher than the saturation temperature. This was followed by decreasing the temperature to the saturation point over 40 min. From this temperature, the solution was cooled at a rate of 0.25 °C per day. After the desired crystal size was obtained, the Rb 3 Ba 3 Li 2 Al B 6 0 2 oF crystal was pulled out of the solution and cooled to room temperature at a rate of 10 °C/h.
  • FTIR Fourier transform infrared spectroscopy
  • UV-vis-NIR diffuse reflectance spectra The UV-vis-NIR diffuse reflectance spectrum was measured at room temperature with a Cary 5000 UV-vis-NIR spectrophotometer in the 200 - 2500 nm wavelength range (see FIG. 11C).
  • SHG Measurement Powder SHG were measured by using the Kurtz-Perry method with Q-switched Nd:YAG lasers at the wavelength of 1064 nm and 532 nm.
  • Refractive Index Measurements A (100) wafer of with size of 7 x 6 x 1 mm 3 was polished using a Unipol-300 grinding/polishing machine (MTI Co.) for the refractive index measurements. The measurements were carried out using a Metricon Model 2010/M prism coupler (Metricon Co.) at 450.2, 532, 636.5, 829.3, and 1062.6 nm.
  • MTI Co. Unipol-300 grinding/polishing machine
  • Laser Damage Threshold Measurement The measurement was carried out on an Nd:YAG nanosecond laser (Model: Minilite II, Continuum Eletro-Optics, Inc.) at a wavelength of 1064 nm.
  • the laser pulse duration was set at 6 ns, and the frequency was fixed at 15 Hz.
  • the laser beam was focused with a convex lens, resulting in a beam diameter of 0.36 mm.
  • FIG. 8 is a schematic illustration of the structural evolution from KBBF to Rb 3 Ba 3 Li 2 Al 4 B 6 0 2 oF.
  • the structural evolution from KBBF to Rb 3 Ba 3 Li 2 Al 4 B 6 0 2 oF may occur because the single-layer structure of KBBF makes it exhibit a strong layer habit.
  • the SBBO family including SBBO, NaCaBe 2 (B0 3 ) 2 F, and K 3 Sr 3 Li 2 Al 4 B 6 0 2 oF, were fabricated. Although the fabricatedmaterials improved the structural stablity of KBBF, the double layers are separated by alkaline-earths, leading to the structrual instability.
  • the 3D Rb 3 Ba 3 Li 2 Al 4 B 6 0 2 oF was fabricated as discussed herein.
  • FIGS. 9A-9C illustrate a TG/DTA curve (FIG. 9A), a recrystallization curve (FIG. 9B), and a photo (FIG. 9C) for NLO materials fabricated according to aspects of the present disclosure.
  • Rb 3 Ba 3 was synthesized and the phase-purity was confirmed by powder X-ray diffraction (PXRD) (FIG. 9A), and thermal analysis indicates that Rb 3 Ba 3 melts congruently with one endothermic (exothermic) peak on heating (cooling) at 856 °C (783 C) (FIG. 9B).
  • the congruent melting behavior is confirmed by the PXRD pattern of the recrystallized Rb 3 Ba 3 melt above 900C.
  • FIGS. 10A-10D are schematics of the building blocks and as-fabricated structure of Rb 3 Ba 3 Li 2 Al 4 B 6 0 2 oF, fabricated according to certain aspects of the present disclosure.
  • FIG. 10A The structure of Rb 3 Ba 3 Li 2 Al 4 B 6 0 2 oF is illustrated broken out into FIG. 10A, the basic building units of Rb 3 Ba 3 Li 2 Al 4 B 6 0 2 oF are BO 3 triangles, AIO4 trahedra, and L1O 3 F tetrahedral; FIG. 10B, illustrating the building units connect with each other to form [LiAl 2 B 3 0iiF] ⁇ layer; FIG. IOC, illustrating the RbOgF and BaOio structures; and FIG. 10D, illustrating that these layers stack along the c axis and connected by Al-O-Al bonding to form 3D framework and Rb and Ba cations filled in the space.
  • Rb 3 Ba 3 is built up from B03 triangles, AIO4 and L1O 3 F tetrahedral, illustrated in FIG. 10A.
  • the BO 3 triangles are co-planar and are linked through oxygen to L1O3F and AIO4 tetrahedra to form a [LiAl 2 B30iiF] ⁇ single layer.
  • the [LiAl 2 B 3 0nF] ⁇ single layer are bridged by Al(l)-0(4) and Li(l)-F(l) bonds to form a [Li 2 Ai 4 B 6 0 2 oF] ⁇ double layer.
  • Table 7 lists atomic coordinates ( lO 4 ) and equivalent isotropic displacement parameters (A 2 x 10 3 ) for Rb 3 Ba 3 Li 2 Al 4 B 6 0 2 oF.
  • U eq is defined as one-third of the trace of the orthogonalized
  • structure of Rb 3 Ba 3 Li 2 Al 4 B 6 0 2 oF exhibits three structural features: 1) All of the B atoms are coordinated in the BO 3 triangles and these BO 3 triangles adopt a coplanar arrangement; 2) The terminal O atoms of BO 3 triangles are bonded by the AIO4/L1O 3 F tetrahedra; 3) the [LiAl 2 B 3 0iiF] ⁇ layers stacking along c axis are connected by Al-0 covalent bonds to form three-dimensional(3D) framework.
  • Rb 3 Ba 3 Li 2 Al 4 B 6 0 2 oF the first two structural features of Rb 3 Ba 3 Li 2 Al 4 B 6 0 2 oF are similar with KBBF and SBBO, which will favor Rb 3 Ba 3 Li 2 Al 4 B 6 0 2 oF to exhibit the excellent NLO properties like KBBF and SBBO.
  • the third structural feature of Rb 3 Ba 3 Li 2 Al B 6 0 2 oF obviously distinguishes from KBBF and SBBO.
  • KBBF contains the [Be 2 B0 3 F 2 ] ⁇ single layers and the [Be 2 B0 3 F 2 ] ⁇ single layers are connected by the weak K-F ion bonds, which lead to the strong layer habit.
  • SBBO series SBBO, NaCaBe 2 (B0 3 ) 2 F and K 3 Ba 3 Li 2 Al 4 B 6 O 20 F all have the double-layer structure.
  • the double-layer structure improves the layer habit of KBBF, the double layers are separated alkaline-earth cations, Ca 2+ , Sr 2+ , or Ba 2+ , which will lead the structural instability or the anisotropic crystal growth.
  • Rb 3 Ba 3 Li 2 Al 4 B 6 0 2 oF all the [LiAl 2 B 3 0nF] ⁇ layers are connected by the Al-0 covalent bonds to form 3D framework.
  • the 3D framework structure will completely resolve the layer habit and structural instability problem in KBBF and SBBO, which has been confirmed by the fact that high quality of bulk Rb 3 Ba 3 Li 2 Al B 6 0 2 oF without layer habit can be grown by the TSSG method.
  • Rb 3 Ba 3 Li 2 Al 4 Be0 2 oF Be 2+ cations, similar with K 3 Ba 3 Li 2 Al 4 Be0 2 oF, are substituted by the Li + /Al + cations. This substitution also makes Rb 3 Ba 3 Li 2 Al B 6 0 2 oF Be- free. Therefore, in this sense, Rb 3 Ba 3 Li 2 Al B 6 0 2 oF would overcome all the crystal growth issues in KBBF and SBBO and represents new generation of deep-UV NLO material.
  • FIGS. 11A-11D illustrate linear and non-linear optical properties of Rb 3 Ba 3 Li 2 Al B 6 0 2 oF fabricated according to certain aspects of the present disclosure.
  • powder second harmonic generation measurements are illustrated in FIG. 11A at 1064 nm and in FIG. 11B at 532 nm reveal that Rb 3 Ba 3 Li 2 Al B 6 0 2 oF is type-1 phase- matchable.
  • the powder SHG measurements of Rb 3 Ba 3 Li 2 Al B 6 0 2 oF with incident radiations at 1064 nm (FIG. 11A) and 532 nm (FIG. 11B) were also performed, respectively.
  • Rb 3 Ba 3 Li 2 Al B 6 0 2 oF has SHG efficiencies of approximately 1.5 x KDP and 0.3 ⁇ ⁇ - ⁇ at 532 nm and 266 nm, respectively, and it can be phase-matchable at both wavelengths.
  • the relative large SHG response will favor its application as the deep-UV NLO material.
  • FIG. l lC is a graph of the reflectance % v. wavelength, and the transmission spectrum indicates the absorption edge of Rb 3 Ba 3 Li 2 Al B 6 0 2 oF is at 198 nm.
  • FIG, 1 ID is a graph of the refractive index measurement that illustrates Rb 3 Ba 3 Li 2 Al B 6 0 2 oF has a moderate birefrigence, 0.057 at 1064 nm.
  • the UV-vis-NIR diffusion reflection spectrum of Rb 3 Ba 3 Li 2 Al B 6 0 2 oF in the 200-2500 nm wavelength range was shown in FIG. 11C.
  • Rb 3 Ba 3 Li 2 Al B 6 0 2 oF has a wide transmission region and the reflectance is higher than 90% from 210 nm to 2500 nm, with a short UV cut-off edge below 200 nm as determined from the UV-vis-IR diffuse-reflectance spectrum (FIG. 11C)).
  • the wide transmission range is comparable with other UV NLO materials, indicating that this material is commercially viable.
  • the refractive index of Rb 3 Ba 3 Li 2 Al 4 B 6 0 2 oF is also measured by the prism coupling method.
  • the measured n 0 and n e at different wavelengths - 450.2, 532, 636.5, 829.3, and 1062.6 nm are listed in Table 8.
  • n 2 2. 54181 + ° " 02028 _ 0 . 00366 2
  • n 2 2. 36263 + — + 0. 0000132 2
  • FIGS. 15A and 15B are before (15A) and after (15B) images of a high quality Rb 3 Ba 3 Li 2 Al B 6 02oF crystal that was placed in water for a week with no decomposition or degradation observed. These properties of Rb 3 Ba 3 Li 2 Al B 6 02oF also satisfy the requirements of deep-UV NLO materials.
  • Rb 3 Ba 3 Li 2 Al B 6 02oF exhibits excellent NLO properties, including relatively large SHG response, -1.5 ⁇ KDP and 0.3 ⁇ ⁇ - BBO at 532 nm and 266 nm, respectively, the short UV cut-off edge, and the suitable birefringence may be about at least 0.06.
  • this compound melts congruently and high quality of single crystal with size of 12 x 8 x 7.6 mm 3 was grown. .
  • Table 9 illustrates wavelengths and refractive indexes for Rb 3 Ba 3 Li 2 Al B 6 02oF fabricated according to certain aspects of the present disclosure. Table 9: Measured and calculated values for Rb 3 Ba 3 Li 2 Al 4 B 6 0 2 oF.
  • a first aspect which is a device comprising a nonlinear optical (NLO) material according to the formula XLi 2 Al 4 B 6 0 2 oF.
  • NLO nonlinear optical
  • a second aspect which is the device of the first aspect, wherein X comprises potassium (K) and strontium (Sr).
  • a third aspect which is the device of the first aspect, wherein X comprises K 3 Sr 3
  • a fourth aspect which is the device of the first aspect, wherein X comprises rubidium
  • a fifth aspect which is the device of the first aspect, wherein X comprises Rb 3 Ba 3 .
  • a sixth aspect which is the device of any of the first through fifth aspects, wherein the NLO exhibits a walkoff of from about 1 mrad to about 200 mrad.
  • a seventh aspect which is the device of any of the first through sixth aspects, wherein the NLO forms single crystals with a minimum diameter of from about 2 mm to about 20 mm in at least two directions.
  • An eighth aspect which is the device of any of the first through seventh aspects, wherein the NLO exhibits a second harmonic generation coefficient of greater than 0.39 pm/V.
  • a ninth aspect which is the device of any of the first through eighth aspects, wherein the NLO exhibits a band gap of greater than 6.2 eV.
  • a tenth aspect which is the device of any of the first through ninth aspects, wherein the NLO exhibits an adsorption edge of less than 200 nm.
  • An eleventh aspect which is the device of any of the first through tenth aspects, wherein the NLO exhibits a laser damage threshold of greater than 5.0 GW/cm 2 .
  • a twelfth aspect which is the device of any of the first through eleventh aspects, wherein the NLO exhibits a bifringence at 1064 nm ranging from about 0.05 to about 0.09.
  • a thirteenth aspect which is a device comprising a nonlinear optical material (NLO) according to the formula KSrCC ⁇ F, wherein the NLO comprises at least one single crystal.
  • NLO nonlinear optical material
  • a fourteenth aspect which is the device of the thirteenth aspect, wherein the NLO exhibits a walkoff of from about 1 mrad to about 200 mrad.
  • a fifteenth aspect which is the device of any of the thirteenth through fourteenth aspects, wherein the NLO forms single crystals with a minimum diameter of from about 2 mm to about 20 mm in at least two directions.
  • a sixteenth aspect which is the device of any of the thirteenth through fifteenth aspects, wherein the NLO exhibits a second harmonic generation coefficient of greater than 0.39 pm/V.
  • a seventeenth aspect which is the device of any of the thirteenth through sixteenth aspects, wherein the NLO exhibits a band gap of greater than 6.2 eV.
  • An eighteenth aspect which is the device of any of the thirteenth through seventeenth aspects, wherein the NLO exhibits an adsorption edge of less than 200 nm.
  • a nineteenth aspect which is the device of any of the thirteenth through eighteenth aspects, wherein the NLO exhibits a laser damage threshold of greater than 5.0 GW/cm 2 .
  • a twentieth aspect which is the device of any of the thirteenth through nineteenth aspects, wherein the NLO exhibits a bifringence at 1064 nm ranging from about 0.05 to about
  • a twenty-first aspect which is a nonlinear optical material selected from the group consisting of KSrC0 3 F
  • a twenty-second aspect which is a device comprising the nonlinear optical material of the twenty-first aspect.
  • R R 1
  • R u any number falling within the range.
  • R Ri+k*(Ru-Ri)
  • k is a variable ranging from 1 percent to 100 percent with a 1 percent increment, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent, 50 percent, 51 percent, 52 percent, 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent.
  • any numerical range defined by two R numbers as defined in the above is also specifically disclosed.

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Abstract

L'invention concerne un dispositif comprenant un matériau optique non linéaire (ONL) selon la formule XLi2Al4B6O20F. L'invention concerne également un dispositif contenant un matériau optique non linéaire (ONL) selon la formule KSrCO3F, l'ONL comprenant au moins un monocristal. L'invention concerne un matériau optique non linéaire choisi dans le groupe constitué par KSrCO3F Rb3Ba3Li2Al4B6O20F et K3Sr3Li2Al4B6O20F.
PCT/US2018/021802 2017-03-10 2018-03-09 Matériau optique non linéaire WO2018165583A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020000541A1 (en) * 1994-07-18 2002-01-03 Takatomo Sasaki Cesium-lithium-borate crystal and its application to frequency conversion of laser light
WO2007127356A2 (fr) * 2006-04-28 2007-11-08 Corning Incorporated Systèmes pulsés de laser raman dans l'ultraviolet et la lumière visible
CN103031605A (zh) * 2011-09-29 2013-04-10 中国科学院福建物质结构研究所 非线性光学晶体氟碳酸锶钾

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020000541A1 (en) * 1994-07-18 2002-01-03 Takatomo Sasaki Cesium-lithium-borate crystal and its application to frequency conversion of laser light
WO2007127356A2 (fr) * 2006-04-28 2007-11-08 Corning Incorporated Systèmes pulsés de laser raman dans l'ultraviolet et la lumière visible
CN103031605A (zh) * 2011-09-29 2013-04-10 中国科学院福建物质结构研究所 非线性光学晶体氟碳酸锶钾

Non-Patent Citations (2)

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Title
KANG ET AL.: "Prospects for Fluoride Carbonate Nonlinear Optical Crystals in the UV and Deep-UV Regions", THE JOURNAL OF PHYSICAL CHEMISTRY C, vol. 117, 18 November 2013 (2013-11-18), pages 25684 - 25692, XP055538469 *
WU ET AL.: "Deep-Ultraviolet Nonlinear-Optical Material K3Sr3Li2Al4B6O20F: Addressing the Structural Instability Problem in KBe2B03F2", INORG. CHEM., vol. 56, no. 15, 25 July 2017 (2017-07-25), pages 8755 - 8758, XP055538470, Retrieved from the Internet <URL:https://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.7b01517> [retrieved on 20180423] *

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